Method of making refractory bodies of tin oxide



Patented Sept. 16, 194i UNITED STATES PATENT OFFICE Dan Moliachlan, In, Corning, N. Y., araignor to Corning Gian izlokrks, Corning ration of New Y N. Y I m- No Drawing. Application 18, 1940,

- Serial No. 336,;

. 40mm. ons-15c) This invention relates to refractories for use' in contact with molten glass and more particularly to refractory bodies composed of or containing substantial amounts of tin oxide.

In a pending application, Serial Number 148,784, filed June 17, 1937, by Harrison P. Hood, it is shown that molded refractory bodies composed of tin oxide are par-ticularly suitable for contact with molten glass and are highly resistant both to the corrosive action of melting batch ingredients and to the erosion of fiowing molten glass. The application further shows that mold- ,ed bodies of tin oxide have a relatively high but slow shrinkage on firing which persists .even after repeated firing and. that the introduction into the tin oxide batch of a small amount of a compound of ametal oi the first, seventh and eighth periodic groups, preferably copper, silver, gold, cobalt, iron, nickel or manganese, accelerates such shrinkage and causes it to be substantially complete in a relatively short time of v firing.

I have found that in slip casting refractory bodies containing tin oxide, the introduction of promoting agents into refractory bodies containing tin oxide.

Another'object is to slip cast bodies containing tin oxide and to incorporate therein a shrinkage promoting agent without detracting from the valuable properties of the final body when fired. Y

, The'above and other objects may be accomplished by practicing my invention which embodies among its features molding a batch containing a substantial amount of tin oxide to form a refractory body, firing the body at a temperature and for a time sumcient to sinter it to a coherent porous mass, impregnating the porous body with a solution containing a shrinkage promoting agent in an amount equivalent, as oxide, to .5%-3% of the weight of the body in a volume of the solution substantially equal tothe pore space 0! the body, drying the impregnated hot: 55 material containing a substantial amount of and firing it in anoxidizing atmosphere at l300-l500 C.

In practicing the invention the refractory batch, which may consist of stannic oxide alone or a mixture thereof with another refractory oxide or oxides including clays, is molded 'in known manner as by pressing under high pressure in a steel mold or preferably by slip casting in a porous mold, after which it is air dried and fired to about l000 0., which temperature I have found su'filcient to sinter the body to a coherent porous mass. The porous body is then impregnated with a solution ,of a shrinking agent consisting preferably of a salt of one of the above recited metals. The amount of shrinking agent introduced, calculated as the oxide of the metal, should be about 5% to 2% of the weight. of the body. To accomplish this the concentration of the solution should be such that a volume thereof equal to the volume of the pore space of the body will contain an amount of the salt equivalent to the required amount of the metal oxide.

The pore space or porosity oi, the body may be determined by measuring the volume of liquid required to fill the pores. v

The impregnated body is air dried and fired in an oxidizing atmosphere to a temperature of i300-l500 C. in increments oi. about 200, each temperature being maintained for about one' hour.

For reasons unknown, the salts comprising the shrinking agents, when introduced into such a refractory body in the amount and in the manner described above, do not eiiioresce or creep to the surface when the body is dried and fired. The composition 0! the body .is therefore substantially the same throughout and shrinkage occurs evenly and uniformly greatly accelerated by the introduction of the agent.

I claim: l. Method of making a refractory body which comprises molding a batch containing a substantial amount of stannic oxide, firing the molded body at a'temperature and for a time sufilcient to sinter it 'to a coherent porous mass, impregnating the porous body with a solution containing a salt of a metal which when raised to sintering' temperatures will accelerate the shrinkage of the refractory, the amount of metal introduced into the body being equivalent, as oxide, to .5%-2% oi the weight of the body, drying the impregnated body and firing it in an oxidizing atmosphere at 1300-1500 C. i

2. Method of making a refractory body from slip casting the material in a porous mold, firing the molded body at a temperature and for a time sufiicient to sinter it to a coherent porous mass, impregnating the porous body with a solution containing a salt of manganese, a volume of the solution substantially equal to the pore space of the body containing an amount of the salt equivalent, as oxide, to .5%-2% of the weight of the body, drying the impregnated bodyand firing it in an oxidizing atmosphere at 1300-1500 C. a

3. Method of molding refractory material containing a substantial amount of finely divided stannic oxide which comprises slip casting the material in a porous mold, firing the molded body at a temperature and for a time suiiicientto sinter it to a coherent porous mass, impregnating .the porous body with'a solution containing a copper salt, a volume of .the solution substantially equal to the pbre'space' oi the body containing an amount oi. the salt equivalent. as I .suflicient to sinter it to a coherent porous mass,

impregnating the porous body with a solution containing a salt of iron, a volume of the solution substantially equal to the pore space of the body containing an amount of the salt equivalent, as oxide, to .5%-2% oi the weight of the -body,,drying the impregnated body and firing it inan oxidizing atmosphere at 1300-1500 C. nan MoLACHLAN, JR. 

